Mold release agent composition

ABSTRACT

A mold release agent composition which contains A) 10 to 95% by weight of a copolymer of a polyfluoroalkyl acrylate or methacrylate ester having a polyfluoroalkyl group having 1 to 20 carbon atoms and a vinyl compound having an alkyl group having 8 to 30 carbon atoms, and B) 90 to 5% by weight of a silicone, has sufficient releasability, has an only slightly amount of the migration to a shaped article and gives no adverse effect on fabricability of a shaped article surface.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a mold release agent composition.Particularly, it relates to a mold release agent composition for themolding, which is suitable for molding a shaped article made of asynthetic resin, a synthetic rubber or the like.

2. Description of Related Art

When a shaped article made of a synthetic resin such as an acrylicresin, an epoxy resin, a urethane resin, a vinyl chloride resin, a vinylacetate resin and a shaped article made of a synthetic rubber areshaped, a mold release agent is coated on an internal surface of a moldso as to facilitate the release of the shaped article from the mold.

As the mold release agent used in such case, for example, wax moldrelease agents such as a paraffin wax, a wax of a higher fatty acidester and a polyethylene wax are known. These wax mold release agentshave been widely used, since they are available with the low cost andgive the resultant shaped article having a good surface state.

However, the wax mold release agent has low releasing strength so thatsufficient release effect cannot be achieved, unless the wax moldrelease agent is thickly coated on the mold when the shaped article isshaped by using a material having high adhesion strength such as anepoxy resin and a urethane resin. Accordingly, the internal surface ofthe mold is contaminated with repeated molding. This problem also givesan adverse effect on the dimensional accuracy of the shaped article.

The wax mold release agent disadvantageously has low adhesion strengthto the mold so that the mold release agent easily migrates to the shapedarticle and has poor continuity of release effect. This problem resultsin that the mold release agent must be coated each time the shaping stepis to be performed.

In addition, when the shaped article is released from the mold, a largeamount of the wax mold release agent migrates to the shaped article sothat the wax mold release agent gives poor fabricability (for example,printing and coating) of the shaped article surface.

As the mold release agent for solving the above problems, afluorine-containing mold release agent a copolymer of a polyfluoroalkylester of (meth)acrylic acid and a substituted vinyl compound! is known(cf. Japanese Patent Kokai Publication Nos. 101319/1984 and255404/1985).

Since the fluorine-containing mold release agent has excellent releasestrength, it give a sufficient release effect by thinly coating it. Thefluorine-containing mold release agent has better adhesion strength tothe mold than the above wax mold release agent so that it givesexcellent continuity to the release effect.

However, even the fluorine-containing mold release agent cannotcompletely prevent the migration to the shaped article surface. Themigration of the fluorine-containing mold release agent to the shapedarticle surface gives an adverse effect on the fabricability (printingor coating) of the shaped article surface. The reason for this is thatthe fluorine-containing mold release agent which migrated to the shapedarticle surface exhibits also the release effect against the ink andpaint used for the printing and coating.

Japanese Patent Kokoku Publication No. 8425/1991 discloses a moldrelease agent which comprises a copolymer obtainable by polymerizing aperfluoroalkyl group-containing vinyl monomer, a phosphoricacid-containing vinyl monomer and a hydrocarbon vinyl monomer. However,since this mold release agent contains a large amount of phosphoricacid, a curing reaction was inhibited in the case of the resin and therubber such as a urethane resin reacting during the molding step so thatthe appearance of the shaped article surface is not good. In addition,the reaction of the mold release agent with the shaped article resultsin the contamination of the mold.

From Japanese Patent Kokoku Publication No. 32514/1984, a mold releaseagent which comprises a mixture of a polyfluoroalkyl group-containingcopolymer and a silicone resin is also known. However, since thesilicone is mixed in a large amount, the shaped article surface issticky and has poor fabricability. The silicone results in the pollutionof the working atmosphere. The silicone-containing mold release agenthas a problem that it gives a sticky shaped article surface and poorfabricability of the shaped article surface when it migrates to theshaped article surface.

SUMMARY OF THE INVENTION

An object of the present invention is to solve the above problems and toprovide a mold release agent having good fabricability of the shapedarticle surface and good releasability.

An aspect of the present invention resides in a mold release agentcomposition comprising A) 10 to 95% by weight of a copolymer of apolyfluoroalkyl acrylate or methacrylate ester having a polyfluoroalkylgroup having 1 to 20 carbon atoms and a vinyl compound having an alkylgroup having 8 to 30 carbon atoms, and B) 90 to 5% by weight of asilicone.

DETAILED DESCRIPTION OF THE INVENTION

When the mold release agent composition of the present invention iscoated on the internal surface of the mold, components A and B are notcompatible with each other. A layer mainly containing the component A isseparated from a layer mainly containing the component B, and thecomponent A mainly plays the adhesion action to the mold and thecomponent B mainly plays the release action from the mold. The vinylcompound having the alkyl group having 8 to 30 carbon atomscopolymerized in the component A entraps the component B due to the longchain alkyl group thereof. Namely, the layer mainly containing thecomponent A is formed on the mold and the layer mainly containing thecomponent B is formed on the shaped article. During the release of theshaped article, the shaped article can be easily released from the mold,since the layer mainly containing the component A does not migrate tothe shaped article surface and the layer mainly containing the componentB is destroyed. The amount of the layer mainly containing the componentB which migrates to the shaped article after the destruction is smallerthan the migration amount in the case that the mold release agent ofsilicone alone is used. Accordingly, the shaped article surface is notsticky and the fabricability of the shaped article surface is notadversely affected.

A specific example of polyfluoroalkyl acrylate or methacrylate esterpreferably used in the present invention is a compound of the formula:

    CH.sub.2 ═CR.sup.1 COOR.sup.2 Rf

wherein

R¹ is a hydrogen atom or a methyl group,

R² is a linear or branched alkylene group having 1 to 10 carbon atoms,

--SO₂ N(R³)R⁴ -- group or --CH₂ CH(OR⁵)CH₂ -- group (wherein R³ is analkyl group having 1 to 10 carbon atoms, R⁴ is a linear or branchedalkylene group having 1 to 10 carbon atoms, and R⁵ is a hydrogen atom oran acyl group having 1 to 10 carbon atoms), and

Rf is a linear or branched polyfluoroalkyl group having 1 to 20 carbonatoms.

Specific examples of such compound are as follows:

CF₃ (CF₂)₇ (CH₂)₁₀ OCOCH═CH₂

CF₃ (CF₂)₇ (CH₂)₁₀ OCOC(CH₃)═CH₂

CF₃ (CF₂)₆ CH₂ OCOCH═CH₂

CF₃ (CF₂)₆ CH₂ OCOC(CH₃)═CH₂

(CF₃)₂ CF(CF₂)₆ (CH₂)₂ OCOCH═CH₂

CF₃ (CF₂)₈ CH₂ OCOCH═CH₂

CF₃ (CF₂)₈ CH₂ OCOC(CH₃)═CH₂

(CF₃)₂ CF(CF₂)₈ (CH₂)₂ OCOCH═CH₂

(CF₃)₂ CF(CF₂)₁₀ (CH₂)₂ OCOCH═CH₂

(CF₃)₂ CF(CF₂)₆ (CH₂)₂ OCOC(CH₃)═CH₂

(CF₃)₂ CF(CF₂)₈ (CH₂)₂ OCOC(CH₃)═CH₂

(CF₃)₂ CF(CF₂)₁₀ (CH₂)₂ OCO(CH₃)═CH₂

CF₃ CF₂ (CF₂)₆ (CH₂)₂ OCOCH═CH₂

CF₃ CF₂ (CF₂)₈ (CH₂)₂ OCOCH═CH₂

CF₃ CF₂ (CF₂)₁₀ (CH₂)₂ OCOCH═CH₂

CF₃ CF₂ (CF₂)₆ (CH₂)₂ OCOC(CH₃)═CH₂

CF₃ CF₂ (CF₂)₈ (CH₂)₂ OCOC(CH₃)═CH₂

CF₃ CF₂ (CF₂)₁₀ (CH₂)₂ OCOC(CH₃)═CH₂

H(CF₂)₈ CH₂ OCOC(CH₃)═CH₂

H(CF₂)₈ CH₂ OCOCH═CH₂

Cl(CF₂ CF₂)₃ CH₂ OCOCH═CH₂

Cl(CF₂ CF₂)₃ CH₂ OCOC(CH₃)═CH₂

Cl(CF₂ CF₂)₄ CH₂ OCOCH═CH₂

Cl(CF₂ CF₂)₄ CH₂ OCOC(CH₃)═CH₂

CF₃ (CF₂)₇ SO₂ N(CH₃)(CH₂)₂ OCOCH═CH₂

CF₃ (CF₂)₇ SO₂ N(C₂ H₅)(CH₂)₂ OCOC(CH₃)═CH₂

(CF₃)₂ CF(CF₂)₈ CH₂ CH(OCOCH₃)CH₂ OCOC(CH₃)═CH₂

(CF₃)₂ CF(CF₂)₈ CH₂ CH(OH)CH₂ OCOCH═CH₂

CF₃ CF₂ (CF₂ CF₂)_(n) CH₂ CH₂ OCOCH═CH₂

(a mixture of compounds in which the values of n are 3 to 5)

Specific examples of the preferable vinyl compound having the alkylgroup having 8 to 30 carbon atoms are compounds of the formulas:

CH₂ ═CR¹ COOR⁶

CH₂ ═CHOR⁶

CH₂ ═CHOCOR⁶

CH₂ ═CHR⁶

wherein

R¹ is the same as defined above, and

R⁶ is an C₈₋₃₀ alkyl group, aralkyl group, alkenyl group, or alkylgroup, aralkyl group or alkenyl group substituted with a hydroxyl groupor carboxyl group.

Specific examples of such compounds are as follows: ##STR1##

The amount of the polyfluoroalkyl acrylate or methacrylate ester ispreferably from 20 to 85% by weight, more preferably from 30 to 70% byweight of the copolymer. If it is smaller than 20% by weight, asufficient effect cannot be obtained and the mold is often contaminated.If it is larger than 85% by weight, the releasability is not good.

The carbon number of the polyfluoroalkyl group is from 1 to 20,preferably from 5 to 20, more preferably from 8 to 20. The carbon numberlarger than 20 is economically unsuitable.

The carbon number of the alkyl group in the vinyl compound having thealkyl group is from 8 to 30, preferably 14 to 30. If it is smaller than8, the releasability is not sufficient, the strength of the copolymerfor entrapping the silicone is low and a large amount of the siliconemigrates to the shaped article so that the fabricability isdeteriorated. If it is larger than 30, the vinyl compound is difficultlyavailable and is commercially unsuitable.

The copolymer may comprise another vinyl compound, for example, butylmethacrylate, ethyl methacrylate, glycidyl methacrylate, 2-hydroxyethylmethacrylate, styrene and cyclohexyl methacrylate, in addition to thepolyfluoroalkyl acrylate or methacrylate ester and the vinyl compoundhaving the alkyl group having 8 to 30 carbon atoms in order to improvethe film formability of the coating and the durability. The amount ofthe other vinyl compound is preferably not larger than 10% by weight ofthe copolymer. If it is larger than 10% by weight, releasability isdeteriorated.

The copolymer according to the present invention can be prepared by anyof the various polymerization reaction types and conditions. The variouspolymerization reaction types include the types such as bulkpolymerization, solution polymerization, suspension polymerization,emulsion polymerization and radiation polymerization.

Specific examples of the silicone used according to the presentinvention are a dimethylpolysiloxane oil, an alkylmethylpolysiloxaneoil, a silicone resin comprising SiO₂ and (CH₃)₃ SiO_(1/2).

In the mold release agent composition according to the presentinvention, a ratio of the copolymer to the silicone is such that thecopolymer is from 10 to 95% by weight and the silicone is from 90 to 5%by weight, preferably the copolymer is from 10 to 90% by weight and thesilicone is from 90 to 10% by weight, more preferably the copolymer isfrom 20 to 70% by weight and the silicone is from 80 to 30% by weight.In the above Japanese Patent Kokoku Publication No. 32514/1984, theamount of the polymer containing the polyfluoroalkyl group in the moldrelease agent composition is limited to 0.1 to 10% by weight of thewhole composition, since a large amount of the polymer gives an adverseeffect on the releasability. However, in the present invention, sincethe polyfluoroalkyl group-containing copolymer comprises the vinylcompound having the alkyl group having 8 to 30 carbon atoms and gives noadverse effect on the releasability, an amount larger than 10% by weightresults in a smaller amount of the silicone and gives a good effect onthe fabricability and stickiness of the shaped article surface.

When the mold release agent composition according to the presentinvention is coated on the mold, any of various coating procedures suchas brushing, dip coating and spray coating can be used. The mold releaseagent composition according to the present invention is preferablydissolved or dispersed in water or an organic solvent, when it is coatedon the mold. After the coating, a drying alone is necessary. Thecomposition may be an aerosol comprising a propellant such as1,1,1,2-tetrafluoroethane and a liquefied petroleum gas.

The mold release agent composition according to the present inventionhas good solubility in various solvents. In particular, when thecopolymer comprising at least 15% by weight of the vinyl compound havingthe alkyl group having 8 to 30 carbon atoms is used, the compositionwhich conventionally dissolved in only a fluorine- orchlorine-containing organic solvent or a hydrocarbon organic solvent canalso dissolve in an organic solvent such as an ester organic solvent anda petroleum organic solvent so that the used solvent can be selectedfrom an extended range of solvents. The concentration of the moldrelease agent composition in water or the organic solvent is generallyfrom 0.001 to 20% by weight, preferably from 0.01 to 3% by weight.

PREFERRED EMBODIMENT OF THE INVENTION

The present invention will be illustrated by the following Examples.

EXAMPLE 1

Copolymer:

(1) CF₃ CF₂ (CF₂ CF₂)_(n) CH₂ CH₂ OCOCH═CH₂ 70 wt %

(a mixture of the compounds in which the values of n are 3, 4 and 5 in aweight ratio of 5:3:1)

(2) C₁₈ H₃₇ OCOCH═CH₂ 30 wt %

A mold release agent composition consisting of the copolymer having theabove composition (3 parts by weight), silicone a (0.5 parts by weight),silicone b (0.5 parts by weight) and isooctane (96 parts by weight) wassubjected to a mold release test. The results shown in Table 3 wereobtained. Further, in order to evaluate the fabricability of a shapedarticle surface, a coating test of the shaped article was conducted. Theresults are shown in Table 3.

EXAMPLES 2 TO 15

Mold release agent compositions shown in Table 1 were subjected to themold release test and the coating test. The results are shown in Table3.

COMPARATIVE EXAMPLES 1 TO 14

Mold release agent compositions shown in Table 2 were subjected to themold release test and the coating test. The results are shown in Table3.

Mold release test

(1) A mold release agent was brush-coated on an aluminum mold having adimension of 6 cm (diameter)×1 cm.

(2) A urethane having the following composition was sufficiently stirredin a mixer and poured into the mold described in (1).

(3) After the urethane was cured at a room temperature for 10 minutes,the releasability was evaluated by pulling a stick which was previouslystood in a shaped article.

1: The shaped article can be released from the mold almost without aforce.

2: The shaped article can be released from the mold with a slight force.

3: The shaped article can be released from the mold with a strong force.

4: The shaped article cannot be released from the mold.

Coating test (Check pattern test)

A coating test was conducted according to JIS D-0202.

(1) The following primer paint was brush-coated on the shaped articlereleased in the mold release test.

(2) After the shaped article was dried at 80° C. for 10 minutes, a checkpattern test was conducted.

(3) Further, the following top coat paint was brush-coated on the shapedarticle.

(4) After the shaped article was dried at 100° C. for 40 minutes, thecheck pattern test was conducted.

    ______________________________________    Composition of urethane    ______________________________________    Polyether polyol having a hydroxyl value of 28.1                               100    pbw    Ethylene glycol            19     pbw    Trichlorofluoromethane     5      pbw    Amine catalyst             0.9    pbw    Dibutyltin dilaurate       0.025  pbw    Diphenylmethanediisocyanate                               104    pbw    Paint (manufactured by Dainippon Paint Co. Ltd.)    Primer paint    Puranito L # 75            100    pbw    Puranito L # 75 Thinner    100    pbw    Top coat paint    Puranito S                 100    pbw    Puranito Thinner # 10      100    pbw    ______________________________________

    TABLE 1      - Copolymer Silicone Emulsifier Solvent      Example 1 Composition of copolymer pbw  pbw  pbw  pbw      1 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2)nCH.sub.2 CH.sub.2 OCOCHCH.sub.2 7     0 wt % 3 Silicone a 0.5 --  Isooctane 96       (a mixture of compounds wherein the values of   Silicone b 0.5               n are 3, 4 and 5 in a weight ratio of 5:3:1)       C.sub.18 H.sub.37      OCOCHCH.sub.2 30 wt %                                 2 CF.sub.3     CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2 OCOCHCH.sub.2 30 wt     % 2 Silicone a 2 --  Decane 96       C.sub.18 H.sub.37      OCOCHCH.sub.2 70 wt %                                 3 CF.sub.3     CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2     OCOC(CH.sub.3)CH.sub.2 50 wt % 3.5 Silicone c 0.5 --  Butyl acetate 96         C.sub.12 H.sub.25      OCOCHCH.sub.2 50 wt %                               4 CF.sub.3 CF.sub.2     (CF.sub.2 CF.sub.2)nCH.sub.2 CH(OCOCH.sub.3)CH.sub.2 OCOCHCH.sub.2 80 wt     % 0.5 Silicone d 3.5 --  Trichloro- 96       C.sub.22 H.sub.45      OCOCHCH.sub.2 20 wt %      trifluoroethane            5 CF.sub.3     CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2      OCOC(CH.sub.3)CH.sub.2 85 wt % 3 Silicone b 1 --  Trichloro- 96               C.sub.10 H.sub.21 OCOCHCH.sub.2 15 wt %      trifluoroethane        6 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2     OCOC(CH.sub.3)CH.sub.2 80 wt % 1 Silicone d 3 --  Trichloro- 96       C.sub.18 H.sub.37 OCOC(CH.sub.3)CH.sub.2 20 wt %      trifluoroethane       7 H(CF.sub.2 CF.sub.2).sub.4 CH.sub.2 OCOCHCH.sub.2 50 wt % 3 Silicone     b 1 --  Petroleum ether 96       C.sub.22 H.sub.45      OCOC(CH.sub.3)CH.sub.2 50 wt %                        8 (CF.sub.3).sub.2      CF(CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH(OH)CH.sub.2 OCOCHCH.sub.2 30 wt     % 3 Silicone b 1 --  Tricloro- 96       C.sub.8 H.sub.17 OCOC(CH.sub.3)CH.sub.2 70 wt %      trifluoroethane        9 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 (CH.sub.2).sub.10     OCOCHCH.sub.2 30 wt % 3 Silicone b 1 --  Xylene 96       C.sub.18 H.sub.37      OCOCHCH.sub.2 70 wt %                                 10 the same as in     Example 1  0.5 Silicone b 0.1 --  Isooctane 99.4      11 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2     OCOCHCH.sub.2 50 wt % 3 Silicone b 1 --  Trichloro- 86       (HO).sub.2 P(O)OCH.sub.2 CH.sub.2 OCOCHCH.sub.2      5 wt %      trifluoroethane       C.sub.10 H.sub.21 OCOCHCH.sub.2 45 wt %      Isopropyl alcohol 10                                                                         12     the same as in Example 1  3      ##STR2##      0.50.5      ##STR3##      0.2 Water 95.8     13 the same as in Example 2  2 Silicone a 2      ##STR4##      0.2 Water 95.8     14 the same as in Example 1  3 Silicone a 0.5 C.sub.7 H.sub.15 CO.sub.2     NH.sub.4 0.03 Water 95.97          Silicone b 0.5      15 the same as in Example 2  2 Silicone a 2 C.sub.7 H.sub.15 CO.sub.2     NH.sub.4 0.03 Water 95.97

    TABLE 2      - Example Copolymer Silicone Emulsifier Solvent      No. Composition of copolymer  pbw Type pbw  pbw Type pbw      Com. 1 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2)nCH.sub.2 CH.sub.2      OCOCHCH.sub.2  4 --  --  Trichloro- 96       (a mixture of compounds wherein the       trifluoro-       values of n are 3, 4 and 5 in a       ethane       weight ratio of 5:3:1)      Com. 2 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2)nCH.sub.2 CH.sub.2      OCOCHCH.sub.2 90 wt % 4 --  --  Trichloro- 96       C.sub.18 H.sub.37      OCOCHCH.sub.2 10 wt %      trifluoro-                         ethane         Com. 3 the same as in Example 1  3.9 Silicone b 0.1 --  Isooctane 96      Com. 4 the same as in Example 1  0.2 Silicone b 3.8 --  Isooctane 96         Com. 5 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2)nCH.sub.2 CH.sub.2     OCOCHCH.sub.2 10 wt % 3.0 Silicone b 1.0 --  Isooctane 96       (a mixture of compounds wherein the       values of n are 3, 4 and 5 in a       weight ratio of 5:3:1)       C.sub.18 H.sub.37      OCOCHCH.sub.2 90 wt %                                 Com. 6 C.sub.8     F.sub.17 CH.sub.2 CH.sub.2 OCOCHCH.sub.2 70 wt % 3 Silicone b 1.0 --     Trichloro- 96       C.sub.6 H.sub.13      OCOCHCH.sub.2 30 wt %      trifluoro-                          ethane        Com. 7 C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)CH.sub.3)CH.sub.2     CH.sub.2 OCOCHCH.sub.2 98 wt % 2.0 Silicone b 2.0 --  Trichloro- 96            C.sub.18 H.sub.37 OCOCHCH.sub.2      2 wt %      trifluoro-                    ethane      Com. 8 CF.sub.3 CF.sub.2 (CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2     OCOCHCH.sub.2 50 wt % 3.0 Silicone b 1.0 --  Trichloro- 96      ##STR5##      50 wt %      trifluoro-ethane     Com. 9 C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2     OCOCHCH.sub.2 50 wt % 4   --  Trichloro-       (HO).sub.2 P(O)OCH.sub.2 CH.sub.2 OCOCHCH.sub.2 30 wt %  --     tirfluror- 86              ethane       C.sub.18 H.sub.37 OCOC(CH.sub.3)CH.sub.2 20 wt %      Isopropyl 10                  alcohol      Com. 10 the same as in Comparative Example 9  2 Silicone b 2 --     Trichloro- 91              trifluoro-              ethane              Isopropyl 5              alcohol      Com. 11 C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2     OCOCHCH.sub.2 65 wt % 2 Silicone a 2 --  Trichloro- 86              trifluoro-       (HO).sub.2 P(O)OCH.sub.2 CH.sub.2 OCOCHCH.sub.2 15 wt %      ethane 10              Isopropyl       C.sub.18 H.sub.37      OCOC(CH.sub.3)CH.sub.2 20 wt %      alcohol           Com. 12 (CF.sub.3)     .sub.2 CF(CF.sub.2).sub.6 (CH.sub.2).sub.3 OCOCHCH.sub.2 73 wt % 0.4     Silicone a 1.6 --  Methylene 96              chloride       C.sub.2 H.sub.5      OCOCHCH.sub.2 25 wt %  Silicone e 2                      CH.sub.3     COCH.sub.2 C(CH.sub.3)NCOCHCH.sub.2      2 wt %                                         Com. 13 the same as in Comparative     Example 1  4 --      ##STR6##      0.2 Water 95.8     Com. 14 the same as in Comparative Example 2  4 --  C.sub.7 F.sub.15     CO.sub.2      NH.sub.4 0.03 Water 95.97     Note)     Silicone a: A silicone resin which comprises (CH.sub.3).sub.3 SiO.sub.1/2     and SiO.sub.2 in a mole ratio of 2:1 and has a molecular weight of about     1,000.     Silicone b: A silicone oil of the formula: (CH.sub.3).sub.3     SiO Si(CH.sub.3).sub.2 O!.sub.n Si(CH.sub.3).sub.3 having a dynamic     viscosity of 350 cSt.     and SiO.sub.2 in a mole ratio of 3:2 and has a molecular weight of about     2,000.     Silicone d: A silicone oil of the formula: (CH.sub.3).sub.3     SiO Si(CH.sub.3).sub.2 O!.sub.n Si(CH.sub.3).sub.3 having a dynamic     viscosity of 1,000 cSt.     ##STR7##

                  TABLE 3    ______________________________________             Mold release                        Coating test             test       (Check pattern test)             Releasability                        Primer   Top coat    ______________________________________    Example  1     1            100/100                                       100/100             2     1            100/100                                       100/100             3     1            100/100                                       100/100             4     1             90/100                                        90/100             5     1            100/100                                       100/100             6     1             90/100                                        90/100             7     1            100/100                                       100/100             8     1            100/100                                       100/100             9     1            100/100                                       100/100             10    2            100/100                                       100/100             11    2            100/100                                       100/100             12    1            100/100                                       100/100             13    1            100/100                                       100/100             14    1            100/100                                       100/100             15    1            100/100                                       100/100    Com. Ex. 1     1             50/100                                        50/100             2     1             50/100                                        50/100             3     1             50/100                                        50/100             4     2             0/100  0/100             5     3            100/100                                       100/100             6     2             50/100                                        50/100             7     1             50/100                                        50/100             8     3             50/100                                        50/100             9     3             50/100                                        50/100             10    3             80/100                                        80/100             11    3             80/100                                        80/100             12    2             0/100  0/100             13    1             50/100                                        50/100             14    1             50/100                                        50/100    ______________________________________     Note) Coating test:     Left values of the data indicate the number of the squares which remained     without completely peeling off from the shaped article, per the 100 (10     × 10) squares of 1 mm × 1 mm formed by cut lines reaching the     substrate.

What is claimed is:
 1. A mold release agent composition comprising:A)12.5 to 95% by weight of a copolymer of a polyfluoroalkyl acrylate ormethacrylate ester having a polyfluoroalkyl group having 1 to 20 carbonatoms and a vinyl compound having an alkyl group having 8 to 30 carbonatoms, wherein the copolymer comprises 20 to 85% by weight of theperfluoroalkyl acrylate or methacrylate ester and 80 to 15% by weight ofthe vinyl compound, and B) 87.5 to 5% by weight of a silicone.
 2. Themold release agent composition according to claim 1, wherein the amountof the copolymer is from 20 to 70% by weight and the amount of thesilicone is from 80 to 30% by weight.
 3. A mold release agentcomposition consisting essentially of:A) 12.5 to 95% by weight of acopolymer of a polyfluoroalkyl acrylate or methacrylate ester having apolyfluoroalkyl group having 1 to 20 carbon atoms and a vinyl compoundhaving an alkyl group having 8 to 30 carbon atoms, wherein the copolymercomprises 20 to 85% by weight of the perfluoroalkyl acrylate ormethacrylate ester and 80 to 15% by weight of the vinyl compound, and B)87.5 to 5% by weight of a silicone.
 4. The mole release agentcomposition according to claim 3, wherein the amount of copolymer isfrom 20 to 70% by weight and the amount of the silicone is from 80 to30% by weight.
 5. The mold release agent composition according to claim1, wherein the perfluoroalkyl acrylate and the methacrylate ester areeach encompassed by the formula CH₂ ═CR¹ COOR² Rf, wherein:R¹ is ahydrogen atom or a methyl group, R² is a linear or branched alkylenegroup having 1 to 10 carbon atoms, --SO₂ N(R³)R⁴ -- or --CH₂ CH(OR⁵)CH₂--, R³ is an alkyl group having 1 to 10 carbon atoms, R⁴ is a linear orbranched alkylene group having 1 to 10 carbon atoms, R⁵ is a hydrogenatom or an acyl group having 1 to 10 carbon atoms, and Rf is a linear orbranched polyfluoroalkyl group having 1 to 20 carbon atoms.
 6. The moldrelease agent composition according to claim 1, wherein the vinylcompound having the alkyl group having 8 to 30 carbon atoms isencompassed by a formula selected from the group consisting of:CH₂ ═CR¹COOR⁶, CH₂ ═CHOR⁶, CH₂ ═CHOCOR⁶ and CH₂ =CHR⁶,wherein: R¹ is a hydrogenatom or a methyl group, R⁶ is a C₈₋₃₀ alkyl group, an aralkyl group, analkenyl group, an alkyl group substituted with a hydroxyl group or acarboxyl group, an aralkyl group substituted with a hydroxyl group or acarboxyl group, or an alkenyl group substituted with a hydroxyl group ora carboxyl group.
 7. The mold release agent composition according toclaim 1, wherein:(a) the perfluoroalkyl acrylate and the methacrylateester are each encompassed by the formula CH₂ ═CR¹ COOR² Rf, wherein:R¹is a hydrogen atom or a methyl group, R² is a linear or branchedalkylene group having 1 to 10 carbon atoms, --SO₂ N(R³)R⁴ -- or --CH₂CH(OR⁵)CH₂ --, R³ is an alkyl group having 1 to 10 carbon atoms, R⁴ is alinear or branched alkylene group having 1 to 10 carbon atoms, R⁵ is ahydrogen atom or an acyl group having 1 to 10 carbon atoms, and Rf is alinear or branched polyfluoroalkyl group having 1 to 20 carbon atoms;and (b) the vinyl compound having the alkyl group having 8 to 30 carbonatoms is encompassed by a formula selected from the group consistingof:CH₂ ═CR¹ COOR⁶, CH₂ ═CHOR⁶, CH₂ ═CHOCOR⁶ and CH₂ ═CHR⁶,wherein: R¹ isa hydrogen atom or a methyl group, R⁶ is a C₈₋₃₀ alkyl group, an aralkylgroup, an alkenyl group, an alkyl group substituted with a hydroxylgroup or a carboxyl group, an aralkyl group substituted with a hydroxylgroup or a carboxyl group, or an alkenyl group substituted with ahydroxyl group or a carboxyl group.
 8. The mold release agentcomposition according to claim 3, wherein the perfluoroalkyl acrylateand the methacrylate ester are each encompassed by the formula CH₂ ═CR¹COOR² Rf, wherein:R¹ is a hydrogen atom or a methyl group, R² is alinear or branched alkylene group having 1 to 10 carbon atoms, --SO²N(R³)R⁴ -- or --CH₂ CH(OR₅)CH₂ --, R³ is an alkyl group having 1 to 10carbon atoms, R⁴ is a linear or branched alkylene group having 1 to 10carbon atoms, R⁵ is a hydrogen atom or an acyl group having 1 to 10carbon atoms, and Rf is a linear or branched polyfluoroalkyl grouphaving 1 to 20 carbon atoms.
 9. The mold release agent compositionaccording to claim 3, wherein the vinyl compound having the alkyl grouphaving 8 to 30 carbon atoms is encompassed by a formula selected fromthe group consisting of:CH₂ ═CR¹ COOR⁶, CH₂ ═CHOR⁶, CH₂ ═CHOCOR⁶ andCH2═CHR6,wherein: R¹ is a hydrogen atom or a methyl group, R⁶ is a C₈₋₃₀alkyl group, an aralkyl group, an alkenyl group, an alkyl groupsubstituted with a hydroxyl group or a carboxyl group, an aralkyl groupsubstituted with a hydroxyl or a carboxyl group, or an alkenyl groupsubstituted with a hydroxyl or a carboxyl group.
 10. The mold releaseagent composition according to claim 3, wherein:(a) the perfluoroalkylacrylate and the methacrylate ester are each encompassed by the formulaCH₂ ═CR¹ COOR² Rf, wherein: R¹ is a hydrogen atom or a methyl group, R²is a linear or branched alkylene group having 1 to 10 carbon atoms,--SO₂ N(R³)R⁴ -- or --CH₂ CH(OR⁵)CH₂ --, R³ is an alkyl group having 1to 10 carbon atoms, R⁴ is a linear or branched alkylene group having 1to 10 carbon atoms, R⁵ is a hydrogen atom or an acyl group having 1 to10 carbon atoms, and Rf is a linear or branched polyfluoroalkyl grouphaving 1 to 20 carbon atoms; and (b) the vinyl compound having the alkylgroup having 8 to 30 carbon atoms is encompassed by a formula selectedfrom the group consisting of: CH₂ ═CR¹ COOR⁶, CH₂ ═CHOR⁶, CH₂ ═CHOCOR⁶and CH₂ ═CHR⁶,wherein: R¹ is a hydrogen atom or a methyl group, R⁶ is aC₈₋₃₀ alkyl group, an aralkyl group, an alkenyl group, an alkyl groupsubstituted with a hydroxyl group or a carboxyl group, an aralkyl groupsubstituted with a hydroxyl group or a carboxyl group, or an alkenylgroup substituted with a hydroxyl group or a carboxyl group.
 11. Themold release agent according to claim 5, wherein the polyfluoroalkylacrylate or methacrylate ester is selected from the group consistingof:CF₃ (CF₂)₇ (CH₂)₁₀ OCOCH═CH₂, CF₃ (CF₂)₇ (CH₂)₁₀ OCO(CH₃)═CH₂, CF₃(CF₂)₆ CH₂ OCOCH═CH₂, CF₃ (CF₂)₆ CH₂ OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₆(CH₂)₂ OCOCH═CH₂, CF₃ (CF₂)₈ CH₂ OCOCH═CH₂, CF₃ (CF₂)₈ CH₂ OCOC(CH₃)═CH₂, (CF₃ )₂ CF(CF₂)₈ (CH₂)₂ OCOCH═CH₂, (CF₃ )₂ CF(CF₂)₁₀ (CH₂)₂OCOCH═CH₂, (CF₃)₂ CF(CF₂)₆ (CH₂)₂ OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₈ (CH₂)₂OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₁₀ (CH₂)₂ OCO(CH₃)═CH₂, CF₃ BCF₂ (CF₂)₆(CH₂)₂ OCOCH═CH₂, CF₃ BCF₂ (CF₂)₈ (CH₂)₂ OCOCH═CH₂, CF₃ BCF₂ (CF₂)₁₀(CH₂)₂ OCOCH═CH₂, CF₃ BCF₂ (CF₂)₆ (CH₂)₂ OCOC(CH₃)═CH₂, CF₃ CF₂ (CF₂)₈(CH₂)₂ OCOC(CH₃)═CH₂, CF₃ CF₂ (CF₂)₁₀ (CH₂)₂ OCOC(CH₃)═CH₂, H(CF₂)₈ CH₂OCOC(CH₃)═CH₂, H(CF₂)₈ CH₂ OCOCH═CH₂, Cl(CF₂ CF₂)₃ CH₂ OCOCH═CH₂, Cl(CF₂CF₂)₃ CH₂ OCOC (CH₃)═CH₂, Cl(CF₂ CF₂)₄ CH₂ OCOCH═CH₂, Cl(CF₂ CF₂)₄ CH₂OCOC(CH₃)═CH₂, CF₃ (CF₂)₇ SO₂ N(CH₃) (CH₂)₂ OCOCH═CH₂, CF₃ (CF₂)₇ SO₂N(C₂ H₅) (CH₂)₂ OCOC(CH₃)═CH₂, (CF₃)₂ CF (CF₂)₈ CH₂ CH(OCOCH₃) CH₂OCOC(CH₃)═CH₂, (CF₃)₂ CF (CF₂)₈ CH₂ CH(OH)CH₂ OCOCH═CH₂ and CF₃ CF₂ (CF₂CF₂)_(n) CH₂ CH₂ OCOCH═CH₂,wherein n is 3 to
 5. 12. The mold releaseagent according to claim 8, wherein the polyfluoroalkyl acrylate ormethacrylate ester is selected from the group consisting of:CF₃ (CF₂)₇(CH₂)₁₀ OCOCH═CH₂, CF₃ (CF₂)₇ (CH₂)₁₀ OCO(CH₃)═CH₂, CF₃ (CF₂)₆ CH₂OCOCH═CH₂, CF₃ (CF₂)₆ CH₂ OCOC (CH₃)═CH₂, (CF₃)₂ CF(CF₂)₆ (CH₂)₂OCOCH═CH₂, CF₃ (CF₂)₈ CH₂ OCOCH═CH₂, CF₃ (CF₂)₈ CH₂ OCOC(CH₃)═CH₂,(CF₃)₂ CF(CF₂)₈ (CH₂)₂ OCOCH═CH₂, (CF₃)₂ CF(CF₂)₁₀ (CH₂)₂ OCOCH═CH₂,(CF₃)₂ CF(CF₂)₆ (CH₂)₂ OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₈ (CH₂)₂OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₆ (CH₂)₂ OCO(CH₃)═CH₂, CF₃ CF₂ (CF₂)₆(CH₂)₂ OCOCH═CH₂, CF₃ CF₂ (CF₂)₈ (CH₂)₂ OCOCH═CH₂, CF₃ CF₂ (CF₂)₁₀(CH₂)₂ OCOCH═CH₂, CF₃ CF₂ (CF₂)₆ (CH₂)₂ OCOC(CH₃)═CH₂, CF₃ CF₂ (CF₂)₈(CH₂)₂ OCOC(CH₃)═CH₂, CF₃ CF₂ (CF₂)₁₀ (CH₂)₂ OCOC(CH₃)═CH₂, H(CF₂)₈ CH₂OCOC(CH₃)═CH₂, H(CF₂)₈ CH₂ OCOCH═CH₂, Cl(CF₂ CF₂)₃ CH₂ OCOCH═CH₂, Cl(CF₂CF₂)₃ CH₂ OCOC(CH₃)═CH₂, Cl(CF₂ CF₂)₄ CH₂ OCOCH═CH₂, Cl(CF₂ CF₂)₄ CH₂OCOC(CH₃)═CH₂, CF₃ (CF₂)₇ SO₂ N(CH₃)(CH₂)₂ OCOCH═CH₂, CF₃ (CF₂)₇ SO₂N(C₂ H₅)(CH₂)₂ OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₈ CH₂ CH(OCOCH₃)CH₂OCOC(CH₃)═CH₂, (CF₃)₂ CF(CF₂)₈ CH₂ CH(OH)CH₂ OCOCH═CH₂ and CF₃ CF₂ (CF₂CF₂)_(n) CH₂ CH₂ OCOCH═CH₂,wherein n is 3 to
 5. 13. The mold releaseagent according to claim 6, wherein the vinyl compound having the alkylgroup having 8 to 30 carbon atoms is selected from the group consistingof:CH₂ ═CHCOOC₈ H₁₇, CH₂ ═CHCOOC₁₀ H₂₁, CH₂ ═CHCOOC₁₂ H₂₅, CH₂ ═CHCOOC₁₈H₃₇, CH₂ ═CHCOOC₂₂ H₄₅, CH₂ ═C(CH₃)COOC₈ H₁₇, CH₂ ═C(CH₃)COOC₁₀ H₂₁, CH₂═C(CH₃)COOC₁₂ H₂₅, CH₂ ═C(CH₃)COOC₁₈ H₃₇, CH₂ ═C(CH₃)COOC₂₂ H₄₅, CH₂═CHCOO--C₆ H₄ --4--C₈ H₁₇, CH₂ ═CHCOO--C₆ H₄ --4--C₁₂ H₂₅, CH₂═CHCOO--C₆ H₄ --4--C₁₈ H₃₇, CH₂ ═C(CH₃)COO--C₆ H₄ --4--C₈ H₁₇, CH₂═C(CH₃)COO--C₆ H₄ --4--C₁₂ H₂₅, CH₂ ═C(CH₃)COO--C₆ H₄ --4--C₁₈ H₃₇, CH₂═C(CH₃)COO--C₆ H₄ --4--C₉ H₁₉, CH₂ ═CHCOO--C₆ H₄ --4--C₉ H₁₉, CH₂ ═CHOC₈H₁₇, CH₂ ═CHOC₁₀ H₂₁, CH₂ ═CHOC₁₂ H₂₅, CH₂ ═CHOC₁₆ H₃₃, CH₂ ═CHOC₁₈ H₃₇,CH₂ ═CHOCOC₈ H₁₇, CH₂ ═CHOCOC₉ H₁₉, CH₂ ═CHOCOC₁₁ H₂₃, CH₂ ═CHOCOC₁₅H₃₀, CH₂ ═CHOCOC₁₇ H₃₅ and CH₂ ═CHC₉ H₁₉.
 14. The mold release agentaccording to claim 9, wherein the vinyl compound having an alkyl grouphaving 8 to 30 carbon atoms is selected from the group consisting of:CH₂═CHCOOC₈ H₁₇, CH₂ ═CHCOOC₁₀ H₂₁, CH₂ ═CHCOOC₁₂ H₂₅, CH₂ ═CHCOOC₁₈ H₃₇,CH₂ ═CHCOOC₂₂ H₄₅, CH₂ ═C(CH₃)COOC₈ H₁₇, CH₂ ═C(CH₃)COOC₁₀ H₂₁, CH₂═C(CH₃)COOC₁₂ H₂₅, CH₂ ═C(CH₃)COOC₁₈ H₃₇, CH₂ ═C(CH₃)COOC₂₂ H₄₅, CH₂═CHCOO--C₆ H₄ --4--C₈ H₁₇, CH₂ ═CHCOO--C₆ H₄ --4--C₁₂ H₂₅, CH₂═CHCOO--C₆ H₄ --4--C₁₈ H₃₇, CH₂ ═C(CH₃)COO--C₆ H₄ --4--C₈ H₁₇, CH₂═C(CH₃)COO--C₆ H₄ --4--C₁₂ H₂₅, CH₂ ═C(CH₃)COO--C₆ H₄ --4--C₁₈ H₃₇, CH₂═C(CH₃)COO--C₆ H₄ --4C₉ H₁₉, CH₂ ═CHCOO--C₆ H₄ --4--C₉ H₁₉, CH₂ ═CHOC₈H₁₇, CH₂ ═CHOC₁₀ H₂₁, CH₂ ═CHOC₁₂ H₂₅, CH₂ ═CHOC₁₆ H₃₃, CH₂ ═CHOC₁₈ H₃₇,CH₂ ═CHOCOC₈ H₁₇, CH₂ ═CHOCOC₉ H₁₉, CH₂ ═CHOCOC₁₁ H₂₃, CH₂ ═CHOCOC₁₅H₃₀, CH₂ ═CHOCOC₁₇ H₃₅ and CH₂ ═CHC₉ H₁₉.